Removing sacrificial material by thermal decomposition

ABSTRACT

A thermally decomposable sacrificial material is deposited in a void or opening in a dielectric layer on a semiconductor substrate. The thermally decomposable sacrificial material may be removed without damaging or removing the dielectric layer. The thermally decomposable sacrificial material may be a combination of organic and inorganic materials, such as a hydrocarbon-siloxane polymer hybrid.

BACKGROUND

The present invention relates generally to the field of integratedcircuit manufacturing, and more specifically, to depositing and removingsacrificial material from voids or openings in a dielectric layer on asemiconductor substrate.

Sacrificial material has been used in integrated circuit manufacturingto fill voids or openings in a dielectric layer on a semiconductorsubstrate. Sacrificial material generally has been a spin-on-polymer(SOP) or spin-on-glass (SOG) that is deposited by spin coating tocompletely fill openings in the dielectric layer. For example,sacrificial material has been used in processes for providing dualdamascene metal interconnects in integrated circuits.

The dual damascene concept involves forming both a via and a trench inthe dielectric layer or interlayer dielectric (ILD). For example, thevia may be etched first. After sacrificial material is deposited to fillthe via and leave between about 500 and 3,000 angstroms of the materialon the surface of the device, the trench is etched. The use ofsacrificial material allows the trench lithography and etching processto effectively apply to a substantially hole-free surface, similar to asurface without vias. Sacrificial material may be selected so that whenthe trench is etched, the sacrificial material may be removed at afaster rate than the dielectric layer.

After etching the trench, any remaining sacrificial material may becleaned out and removed from the via by a combination of plasmaprocessing and wet chemistry steps. Depending on the type of sacrificialmaterial used, various wet etch chemistries may be used to remove theremaining sacrificial material, including buffered oxide etch processesor chemistry based on commercially available amine based materials.After the remaining sacrificial material is removed, the via and trenchmay be filled with a conductive material such as copper to form acomplete conductive layer of interconnects. Chemical metal polishing(CMP) then may be performed to remove excess material and planarize thesurface.

Although the various chemical etch steps for dissolution of thesacrificial material may have high selectivity for sacrificial materialover dielectric material, they nevertheless can damage or removedielectric materials used for the ILD. Dielectric materials with lowerdielectric constants (K) are needed to reduce capacitive coupling andcross talk between adjacent metal lines in dual damascene structures.However, as the ILD dielectric constant is reduced, ILD resistance todamage during cleaning and removal of sacrificial material also isreduced. Thus, for dual damascene interconnects to realize their fullpotential, especially in sub 0.25 micron process technology, the problemof damage to the dielectric layer during removal and cleaning ofsacrificial material must be addressed.

Thus, there is a need for sacrificial material that can be used to fillvoids or openings in a dielectric layer and can be removed or cleanedout without also damaging or removing the dielectric. There is a need toreduce defects and improve yield by enabling a more efficient andeffective cleaning procedure to remove sacrificial material in ILDmaterials and especially ILD materials with low dielectric constants.There is a need for dual damascene process that enables use of ILDmaterials having lower dielectric constants.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 a-1 d illustrate cross-sections that reflect structures that mayresult after certain steps are used to make a copper containing dualdamascene device following one embodiment of the present invention.

FIGS. 2 a-2 d illustrate cross-sections that reflect structures that mayresult after certain steps are used to make a copper containing dualdamascene device following a second embodiment of the present invention.

FIG. 3 illustrates a block diagram of a process according to oneembodiment of the present invention.

FIG. 4 illustrates a block diagram of a process according to anotherembodiment of the present invention.

DETAILED DESCRIPTION

Set forth below is a description of several embodiments of the presentinvention, presented in the context of a semiconductor device thatincludes a copper containing dual damascene interconnect. Thedescription is made with reference to FIGS. 1 a-1 d and FIGS. 2 a-2 dwhich illustrate cross-sections of structures that result after usingcertain steps according to certain embodiments of the invention, andFIGS. 3 and 4 which are flow diagrams of processes according toembodiments of the invention. Although a dual damascene interconnect isdescribed, it will be understood that the present invention also may beused in the context of other semiconductor devices, including but notlimited to single damascene processes, in which sacrificial material maybe used to fill voids or openings in a dielectric layer.

FIG. 1 a shows substrate 101 with first conductive layer 102, barrierlayer 103, and dielectric layer or ILD 104. The substrate may be anysurface, generated when making an integrated circuit, upon which aconductive layer may be formed. The substrate thus may include, forexample, active and passive devices that are formed on a silicon wafersuch as transistors, capacitors, resistors, diffused junctions, gateelectrodes, local interconnects, etc. The substrate also may includeinsulating materials (e.g., silicon dioxide, either undoped or dopedwith phosphorus (PSG) or boron and phosphorus (BPSG); silicon nitride;silicon oxynitride; or a polymer) that separate such active and passivedevices from the conductive layer or layers that are formed on top ofthem, and may include previously formed conductive layers.

The first conductive layer preferably comprises copper, and may beformed using a conventional copper electroplating process, in which acopper layer is formed on barrier and seed layers. The first conductivelayer also may be made from other materials conventionally used to formconductive layers for integrated circuits. For example, the firstconductive layer may be made from a copper alloy, aluminum or analuminum alloy, such as an aluminum/copper alloy. Alternatively, thefirst conductive layer may be made from doped polysilicon or a silicide,e.g., a silicide comprising tungsten, titanium, nickel or cobalt. Thefirst conductive layer may include a number of separate layers. Forexample, the first conductive layer may comprise a primary conductormade from an aluminum/copper alloy that is sandwiched between arelatively thin titanium layer located below it and a titanium, titaniumnitride double layer above it. The first conductive layer may be formedby a chemical vapor or physical deposition process, like those that arewell known to those skilled in the art. If copper is used to make thefirst conductive layer, a conventional copper electroplating process maybe used. Although a few examples of the types of materials that may formthe first conductive layer have been identified here, it may be formedfrom various other materials that can serve to conduct electricitywithin an integrated circuit. Although copper is preferred, the use ofany other conducting material, which may be used to make an integratedcircuit, falls within the spirit and scope of the present invention.

The barrier layer may be made from silicon nitride, but also may be madefrom other materials such as titanium nitride or oxynitride, as is wellknown to those skilled in the art. When formed from silicon nitride, achemical vapor deposition process may be used to form the barrier layer.The barrier layer may serve to prevent an unacceptable amount of copper,or other metal, from diffusing into other layers, and also may act as anetch stop to prevent subsequent via and trench etch steps from exposingthe first conductive layer to subsequent cleaning steps. The barrierlayer should be thick enough to perform its diffusion inhibition andetch stop functions, but not so thick that it adversely impacts theoverall dielectric characteristics resulting from the combination of thebarrier layer and the dielectric layer overlying the barrier layer. Thethickness of the barrier layer preferably should be less than about 10%of the thickness of the overlying dielectric layer, and preferablybetween about 100 and 500 angstroms thick.

In one embodiment, the dielectric layer has a dielectric constant lowerthan 3.9 which is the dielectric constant of silicon dioxide. Forexample, the dielectric layer may comprise plasma enhanced chemicalvapor deposition (PECVD) silicon dioxide doped with carbon, having adielectric constant of approximately 2.2 to 2.6. Other materials thatmay be used for the dielectric layer include materials that may insulateone conductive layer from another, and preferably those materials havingdielectric constants below that of silicon dioxide, and most preferablymaterials with dielectric constants below 3.0. For example, thedielectric layer may comprise fluorinated silicon dioxide or organicpolymers selected from the group that includes polyimides, parylenes,polyartylethers, polynaphthalenes, and polyquinolines, or copolymersthereof. The dielectric layer preferably has a thickness of betweenabout 2,000 and about 20,000 angstroms.

In one embodiment of the invention, as shown in FIG. 1 a, via 105 isetched into the dielectric layer. To etch the via, a photoresist layermay be patterned on top of the dielectric layer to define the viaformation region, using conventional photolithographic techniques, suchas masking a layer of photoresist, exposing the masked layer to light,then developing the unexposed portions. Alternatives to photoresist alsomay be used, including a bi- or multi-layer photolithographic process,imprinting, electron beam, x-ray atomic force microscopy (AFM), or otherforms of advanced lithography. Conventional process steps for etchingthrough a dielectric layer may be used to etch the via, e.g., aconventional anisotropic dry oxide etch process. For example, the viamay be etched using a medium density magnetically enhanced reactive ionetching system (MERIE system) using fluorocarbon chemistry, or a forminggas chemistry, e.g., one including nitrogen and either hydrogen oroxygen.

As shown in FIG. 1 b, thermally decomposable sacrificial material isused to fill via 105. In one embodiment, the thermally decomposablesacrificial material may be deposited by spin coating between about 500and about 3,000 angstroms of the material onto the surface of thedevice. The spin coating process causes the thermally decomposablesacrificial material to substantially or completely fill the via, with athin layer of the material on the surface of the device.

In one embodiment, the thermally decomposable sacrificial material maybe a combination of inorganic and organic materials, such assilicon-containing and carbonaceous materials. For example, thethermally decomposable sacrificial material may be ahydrocarbon-siloxane polymer hybrid. The siloxane oligomers may beeither main chain or side chains (grafted) in the copolymers. Theseinclude, but are not limited to, silicon containing graft-copolymerssuch as polysiloxane with an oligopolyolefin, oligopolycyclolefin,oligopolyarylolefin, or oligopolycarbonate graft, and combinationsthereof. Additionally, these include polyolefin, polycyclolefin,oligopolyarylolefin, or oligopolycarbonate, or combinations thereof,with an oligosiloxane graft.

The following chart lists examples of other thermally decomposablehydrocarbon containing oligomers and polymers that may be used to formgraft-copolymers, along with their thermal decomposition temperatures(Td) in degrees Centigrade. Polymer Basis or Family Td Polypropyleneoxide   325 to 375 C. Polymethlystyrene   350 to 375 C. Polycaprolactone  325 C. Polycarbonate   325 to 375 C. Polyamideimide   343 C.Polyamide-6,6   302 C. Polyphthalamide   350 C. Polyetherketone   405 C.Polyethretherketone   399 C. Polybutyllene terephthalate   260 C.Polyethyllne terephthalate   300 C. Polystyrene   260 C.Polystyrene-syndiotactic >320 C. Polyphenylene Sulfide   332 C.Polyether Sulfone   400 C.

Other examples of thermally decomposable sacrificial material, accordingto various embodiments of the invention, include polynorbornene withpendant siloxane moieties, marketed under the name UNITY, and/or relatedpolyolefins, and polycarbonate, polyether, and poly(alphamethyl)styrenebased compounds that undergo smooth thermal decomposition. Otherexamples of inorganic polymers and oligomers that may be used asthermally decomposable sacrificial material includehydrosilsesquioxanes, silsesquioxanes and carboranes. Thus, thethermally decomposable sacrificial material includes polymers that maybe thermally decomposed, and may contain both organic and inorganicmoieties, as well as differing levels of organic and inorganic species.

In one embodiment, the thermally decomposable sacrificial material mayinclude polymer blends such as a siloxane polymer and cycololefin typepolymer. If the blending of polymers results in a multiphase mixture,the size of the phase domains may be controlled and/or uniformlydistributed.

In one embodiment, the thermally decomposable sacrificial material mayinclude or be associated with a light absorbing material or dye. Bydyeing the sacrificial material, changes in substrate reflectivity maybe reduced, which may enable the photolithographic process to produceimproved results. In one embodiment, for example, the dye may beassociated to the copolymer through the hydrocarbon polymer portion ofthe hybrid components. Alternatively, the dye may be bonded to thesiloxane component or admixture.

In one embodiment, as shown in FIG. 1 c, trench 107 may be formed in thedielectric layer by lithographic and dry etch process steps. The etchingprocess is applied for a time sufficient to form an opening in thedielectric layer and at least partially into the thermally decomposablesacrificial material to a desired depth. The trench etching process mayremove some of the sacrificial material from the via.

In one embodiment, thermally decomposable sacrificial material 106 aremaining in the via may be removed by thermal decomposition. This maybe accomplished by heating the structure, preferably to a temperature nogreater than 450 degrees C., and preferably in a reducing atmosphere.The thermal decomposition may occur in furnace 108. The thermallydecomposable sacrificial material may be removed by thermaldecomposition without damaging or removing the dielectric material.

The thermal decomposition reaction to remove the remaining thermallydecomposable sacrificial material may also create a solubilitydifference between the pre-decomposition material and anypost-decomposition residue, or enhanced solubility in thepost-decomposition residue by virtue of mass loss and/or surface areaincrease. In addition to being removable by thermal decomposition, thesacrificial material is thermally stable at the temperatures that aretypically used for lithography, reactive ion etch (RIE) and resistremoval in wet chemistries. These temperatures are typically less than150 degrees C.

In one embodiment of the invention, a catalyst may facilitate thermaldecomposition of the organic component of the thermally decomposablesacrificial material. For example, the catalysts that may be usedinclude acids, bases, and thermally or photochemically generated acidsand bases, as well as acids and bases that may be liberated uponexposure to various forms of radiation. The application of catalystsensitive linkages within the polymer structure may facilitatecontrolled decomposition of the thermally decomposable sacrificialmaterial.

In one embodiment, as shown in FIG. 1 d, the trench and via are filledwith second conductive layer 109. A portion of the barrier layer thatseparates the via from the first conductive layer may be removed toexpose the first conductive layer. A CMP step may be used to removeexcess conductive material and planarize the surface of the secondconductive layer. Although FIG. 1 d shows only one dielectric layer andtwo conductive layers, the process described above may be repeated toform additional conductive and insulating layers until the desiredintegrated circuit is produced.

FIGS. 2 a-2 d represent structures that may be formed when applying asecond embodiment of the present invention. FIG. 2 a shows a structuresimilar to the one shown in FIG. 1 a, including substrate 201, firstconductive layer 202, barrier layer 203, and dielectric layer 204,except that trench 205 is formed in the dielectric layer. As shown inFIG. 2 b, thermally decomposable sacrificial material 206 may be appliedto the device, e.g., by spin coating it onto the device's surface, tofill the trench and also create a substantially planar surface over thedevice.

As shown in FIG. 2 c, via 207 is then patterned and etched through theexposed portion of the thermally decomposable sacrificial material andthrough the underlying portion of the dielectric layer. Remainingthermally decomposable sacrificial material 206 a is removed from thetrench by thermal decomposition, i.e., in furnace 208. In FIG. 2 d,second conductive layer 209 is applied to fill the via and trench, whichthen may be planarized.

FIG. 3 illustrates a flow diagram of a process which may be performedaccording to one embodiment of the invention. In block 301, a firstopening is formed in a dielectric layer on a substrate. In block 302,thermally decomposable sacrificial material is deposited in the firstopening. In block 303, a second opening is formed in the dielectriclayer and at least partially in the thermally decomposable sacrificialmaterial. In block 304, the substrate is heated to a temperaturesufficient to remove additional thermally decomposable sacrificialmaterial that remains in the first opening.

FIG. 4 is a block diagram illustrating another embodiment of theinvention. In block 401, a conductive layer is formed on a substrate. Inblock 402, a dielectric layer or ILD is formed over the conductivelayer. The dielectric layer is preferably material having a dielectricconstant below that of silicon dioxide.

In block 403, a via is etched into the dielectric layer. To etch thevia, a photoresist layer may be patterned on top of the dielectric layerusing conventional photolithographic techniques, such as masking thelayer of photoresist, exposing the masked layer to light, thendeveloping the unexposed portions. The via then may be etched throughthe dielectric layer using a conventional anisotropic dry oxide etchprocess. For example, the via may be etched using a medium densitymagnetically enhanced reactive ion etching system (MERIE system) usingfluorocarbon chemistry, or a forming gas chemistry, e.g., one includingnitrogen and either hydrogen or oxygen.

In block 404, the via is filled with thermally decomposable sacrificialmaterial. The thermally decomposable sacrificial material is materialthat may be thermally decomposed and evaporated at an acceptabletemperature, preferably less than 450 degrees C., in a reducingatmosphere, so that it can be removed without damaging dielectricmaterial with a low dielectric constant. The thermally decomposablesacrificial material may be deposited by spin coating between about 500and about 3,000 angstroms of the material onto the surface of thedevice. The spin coating process causes the thermally decomposablesacrificial material to substantially or completely fill the via, with athin layer coating the surface of the device.

In block 405, a trench is etched in the dielectric layer usingphotolithographic and etching steps. In block 406, remaining oradditional sacrificial material may be removed by thermal decompositionin a furnace. In block 407, the trench and via may be filled withconductive material to form a second conductive layer, and the surfaceplanarized. The portion of the barrier layer at the bottom of the viaalso may be removed to expose the first conductive layer to the secondconductive layer.

While the present invention has been described with respect to a limitednumber of embodiments, those skilled in the art will appreciate numerousmodifications and variations therefrom. It is intended that the appendedclaims cover all such modifications and variations as fall within thetrue spirit and scope of this present invention.

1-15. (Canceled).
 16. An apparatus comprising: a semiconductor substratehaving a conductive layer, a barrier layer over the conductive layer,and a dielectric layer over the barrier layer; a first opening and asecond opening etched into the dielectric layer, at least one of theopenings extending through the dielectric layer to the barrier layer;and a thermally decomposable sacrificial material in at least one of thefirst and second openings, wherein the first opening is a via and thesecond opening is a trench in a dual damascene interconnect.
 17. Anapparatus comprising: a semiconductor substrate having a conductivelayer, a barrier layer over the conductive layer, and a dielectric layerover the barrier layer; a first opening and a second opening etched intothe dielectric layer, at least one of the openings extending through thedielectric layer to the barrier layer; and a thermally decomposablesacrificial material in at least one of the first and second openings,wherein the dielectric layer has a dielectric constant below 3.9. 18.The apparatus of claim 17 wherein the dielectric layer has a dielectricconstant in the range of 2.2 to 2.6.
 19. An apparatus comprising: asemiconductor substrate having a conductive layer, a barrier layer overthe conductive layer, and a dielectric layer over the barrier layer; afirst opening and a second opening etched into the dielectric layer, atleast one of the openings extending through the dielectric layer to thebarrier layer; and a thermally decomposable sacrificial material in atleast one of the first and second openings, wherein the thermallydecomposable sacrificial material is a hydrocarbon-siloxane polymerhybrid.
 20. An apparatus comprising: a semiconductor substrate having aconductive layer, a barrier layer over the conductive layer, and adielectric layer over the barrier layer; a first opening and a secondopening etched into the dielectric layer, at least one of the openingsextending through the dielectric layer to the barrier layer; and athermally decomposable sacrificial material in at least one of the firstand second openings, wherein the thermally decomposable sacrificialmaterial is light absorbing.
 21. The apparatus of claim 16 wherein thedielectric layer has a dielectric constant below 3.9.
 22. The apparatusof claim 16 wherein the dielectric layer has a dielectric constant inthe range of 2.2 to 2.6.
 23. The apparatus of claim 16 wherein thethermally decomposable sacrificial material is a hydrocarbon-siloxanepolymer hybrid.
 24. The apparatus of claim 16 wherein the thermallydecomposable sacrificial material is light absorbing.
 25. The apparatusof claim 17 wherein the first opening is a via and the second opening isa trench in a dual damascene interconnect.
 26. The apparatus of claim 19wherein the first opening is a via and the second opening is a trench ina dual damascene interconnect.
 27. The apparatus of claim 19 wherein thedielectric layer has a dielectric constant below 3.9.
 28. The apparatusof claim 20 wherein the first opening is a via and the second opening isa trench in a dual damascene interconnect.
 29. The apparatus of claim 20wherein the dielectric layer has a dielectric constant below 3.9.